Polymer compositions and moulded bodies made therefrom

ABSTRACT

The invention relates to a polymer composition comprising a biologically degradable polymer and a material from sea plants and/or shells of sea animals or at least two components selected from the group consisting of saccharides and the derivatives thereof, proteins, amino acids, vitamins and metal ions. The invention additionally relates to a molded article comprising said polymer composition. Said molded article may be used packaging material or fibrous material, in the form of fibrous material as mixing component for the production of yarns, and in the form of fibrous material for the production of nonwoven fabrics or woven fabrics.

[0001] The invention relates to a polymer composition comprising abiologically degradable polymer, as well as to the use thereof of theproduction of a molded article, the molded article produced from saidpolymer composition, a method for the production thereof and the usethereof, and to an article of clothing comprising the molded article inform of fibers.

[0002] Polymer compositions with different additives for the productionof molded articles are known.

[0003] U.S. Pat. No. 5,766,746 describes a nonwoven fabric made ofcellulose fibers, which comprise a flame-resistant phosphoric component.

[0004] U.S. Pat. No. 5,565,007 describes modified rayon fibers, with amodifying agent for improving the dyeing properties of the fibers.

[0005] U.S. Pat. No. 4,055,702 discloses melt-spun, cold-drawn fibersfrom a synthetic organic polymer with additives. Said additives may bereceptors, flame-resistant rendering agents, antistatic agents,stabilizers, mildew inhibitors or antioxidants.

[0006] “Lenzinger Berichte”, 76/97, page 126 moreover discloses alyocell fiber spun from a cellulose solution inN-methylmorpholine-N-oxide (hereinafter called “NMMNO”), into which maybe incorporated 0.5 to 5 weight-%, relative to the cellulose weight, ofcross-linking agents for improving the wet abrasion value. It isadditionally described to incorporate lyocell fibers,carboxymethylchitin, carboxymethylchitosan or polyethylene imine forimproving the fungicidal properties, polyethylene imine for theadsorption of metal ions and dyes, hyaluronic acid for improving thebactericidal properties, xanthene, guar, carubin, bassorin or starch forimproving hydrophilicity, water adsorption and water vapor permeability,or starch for the accelerated enzymatic hydrolysis.

[0007] WO 98/58015 describes a composition contaning fine particles ofsolid matter for the addition to a formable solution of cellulose in anaqueous tertiary amine oxide. The composition is made of solidparticles, tertiary amine oxide, water and at least another substance.Said other substance may be a stabilizer or a dispersing agent. Thesolid particles may be pigments.

[0008] Furthermore, it is known that high concentrations of iron andtransitional metals influence the stability of a spinning mass ofcellulose, NMMNO and water. High iron concentrations decrease thedisintegration temperature of the solution to such an extent thatexplosion-like disintegration reactions of the solution may occur. Thedisintegration and stabilization of cellulose solved in NMMNO isdescribed in “Das Papier”, F. A. Buitenhuijs 40. year, volume 12, 1986,which also mentions the influence of iron—Fe(III) on said cellulosesolutions. With an addition of 500 ppm of Fe(III) more than 40% of theNMMNO were transformed into the disintegration productN-methylmorpholine (“NMM”), whereby the addition of Cu⁺² also reducesthe stability of the solution. With the addition of copper to an NMMOcellulose solution free of copper the disintegration temperature (Tonset ° C.) was reduced from 175° C. to 114° C. in the presence of 900mg copper/kg of the mass. Moreover described is the positive effect ofstabilizers such as propyl gallate and ellagic acid.

[0009] The addition of additives to fibers moreover causes difficultiesin preserving the properties of the fibers such as mechanicalstabilities, fiber elongations, loop strength, abrasion resistance, dyereceptivity.

[0010] JP 1228916 describes a film made of two layers of woven materialor nonwoven fabric, between which fine flakes of algae material such asRhodophyceae are filled by means of adhesives or by hot welding. Thus, afilm is obtained which, when used, improves the health.

[0011] Said film has, however, the disadvantage that the finely grounded(comminuted) algae material is present in hollow spaces between said twolayers, so that the algae material escapes when the film is torn and isseparated from the environment by the layers.

[0012] U.S. Pat. Nos. 4,421,583 and 4,562,110 describe a method, whereinfiber material is produced from alginate. For this purpose, alginate isobtained from the sea plants by means of an extraction method, and theso obtained soluble alginate is directly spun to form fibers.

[0013] DE 19544097 describes a method of producing molded articles frompolysaccharide mixtures by dissolving cellulose and a secondpolysaccharide in an organic polysaccharide solvent mixable with water,which may likewise contain a second solvent, by molding the solutionunder pressure through a nozzle to form molded articles and bysolidifying the molded articles by means of coagulation in a coagulatingbath. Apart from cellulose, hexoses with glycosidic 1,4 and 1,6 linkage,uronic acids and starch, especially pullulan, carubin, buaran,hyaluronic acid, pectin, algin, carrageenan or xanthene are mentionedtherein as second polysaccharides. Moreover, it is described that, apartfrom a second polysaccharide, also a third polysaccharide, preferablychitin, chitosan or, respectively, a corresponding derivative may beused. The molded articles obtained according to this method are used asmeans for binding water and/or heavy metals, as fiber havingbactericidal and/or fungicidal properties or as yarn with an increaseddegradation velocity in the stomach of ruminants.

[0014] The use of nucleation agents in the production of molded articlesfrom thermoplastic high polymers, especially α-olefinic polymers isdescribed in U.S. Pat. No. 3,367,926. As nucleation agents amino acids,the salts thereof and proteins are, inter alia, mentioned.

[0015] For reducing the fibrillation tendency in cellulosic moldedarticles it is known to apply defibrillation agents on the freshly spunor dried fiber in a subsequent treatment step. All previously knowndefibrillation agents are cross-linking agents.

[0016] According to EP-A-0 538 977 cellulose fibers are treated in analkaline medium with a chemical reagent comprising 2 to 6 functionalgroups capable of reacting with cellulose, in order to reduce thefibrillation tendency.

[0017] Another method for the reduction of the fibrillation tendency ofcellulosic molded articles by means of a textile auxiliary agent isdescribed in WO 99/19555. So far a solution for reducing thefibrillation of the cellulose fibers during the spinning process has notas yet been found.

[0018] It is, therefore, the object of the present invention to providea polymer composition containing an additive, with a good stability andproccesability, as well as a molded article produced therefrom having asmall fibrillation tendency, and a method for the production thereof.

[0019] This object is solved by a polymer composition comprising abiologically degradable polymer and a material from sea plants and/orshells of sea animals, by a molded article produced therefrom as well asby a method for the production thereof according to claims 1 to 6 and 12to 25.

[0020] The object is additionally solved by a polymer compositioncomprising a biologically degradable polymer and at least two componentsselected from the group consisting of saccharides and the derivativesthereof, proteins, amino acids, vitamins and metal ions, by a moldedarticle produced therefrom and by a method for the production thereofaccording to claims 7 to 25.

[0021] The biologically degradable polymer is preferably selected fromthe group consisting of cellulose, modified cellulose, latex, vegetableor animal protein, especially cellulose, and mixtures thereof.Polyamides, polyurethanes and mixtures thereof may likewise be used, asfar as they are biologically degradable. The polymer compositionaccording to the invention and the molded article produced therefrompreferably contain no polymers which are not biologicallynon-degradable, or mixtures thereof.

[0022] The polymer compositions according to the invention may alsocontain polymers which are not biologically degradable. Certain polymersolvents such as DMAc, DMSO or DMF etc. can also solve syntheticpolymers such as aromatic polyamides (aramides), polyacrylonitrile(PACN) or polyvinyl alcohols (PVA), which, again, may be combined toform polymer compositions in combination with known cellulose solventssuch as LiCl/DMAc, DMSO/PF, tertiary amine oxides/water.

[0023] Examples for modified cellulose include carboxethyl cellulose,methyl cellulose, nitrate cellulose, copper cellulose, viscosexanthogenate, cellulose carbamate and cellulose acetate. Examples forfibers from polycondensation and polymerization products are polyamidessubstituted with methyl, hydroxy or benzyl groups. Examples forpolyurethanes are those formed on the basis of polyesterpolyolen.

[0024] The sea plant material is preferably selected from the groupconsisting of algae, kelp and seaweed, especially algae. Examples foralgae include brown algae, green algae, red algae, blue algae ormixtures thereof. Examples for brown algae are Ascophyllum spp.,Ascophyllum nodosum, Alaria esculenta, Fucus serratus, Fucus spiralis,Fucus vesiculosus, Laminaria saccharine, Laminaria hyperborea, Laminariadigitata, Laminaria echroleuca and mixtures thereof. Examples for redalgae include Asparagopsis armata, Chondrus cripus, Maerl beaches,Mastocarpus stellatus, Palmaria palmata and mixtures thereof. Examplesfor green algae are Enteromorpha compressa, Ulva rigida and mixturesthereof, Examples for blue algae are Dermocarpa, Nostoc, Hapalosiphon,Hormogoneae, Porchlorone. A classification of algae can be inferred fromthe Botanic Textbook for Colleges [Lehrbuch der Botanik für Hochschulen]E. Strasburger; F. Noll; H. Schenk; A. F. W. Schimper; 33. edition,Gustav Fischer Verlag, Stuttgart-Jena-New York; 1991.

[0025] The sea plant material can be obtained in different ways. Atfirst, it is harvested, whereby there are three different harvestingmethods:

[0026] 1. the sea plant material washed ashore is collected,

[0027] 2. the sea plants are cut from stones, or

[0028] 3. the sea plants are collected in the sea by divers.

[0029] The sea plant material obtained according to the third method hasthe best quality and is rich in vitamins, minerals, minor elements andpolysaccharides. For the purpose of the present invention the sea plantmaterial harvested according to this method is preferably used.

[0030] The harvested material can be processed in different ways. Thesea plant material can be dried at temperatures of up to 450° C. andgrounded by using ultrasound, wet ball mills, pin-type mills orcounterrotating mills, whereby a powder is obtained, which may, ifrequired, still be subjected to cycloning for the classifying thereof. Aso obtained powder may be used according to the invention. Said seaplant material powder may, in addition, be subjected to an extractionmethod, for instance, with vapor, water or an alcohol such as ethanol,whereby a liquid extract is obtained. Said extract may likewise be usedaccording to the invention.

[0031] The harvested sea plant material can moreover be subjected to acryocomminution, whereby it is comminuted into particles ofapproximately 100 μm at −50° C. If desired, the so obtained material mayadditionally be comminuted, whereby particles having a size ofapproximately 6 to approximately 10 μm are obtained.

[0032] The material from the outer shell of sea animals is preferablyselected out of sea sediments, grounded shells of crabs or mussels,lobsters, crustaceans, shrimps, corals.

[0033] A typical composition of a mixture of natural origin is shown intable 1. TABLE 1 Components (%) Vitamins 0.2% Proteins 5.7% Fats 2.6%Humidity 10.7% Ash 15.4% Carbohydrates 65.6%

[0034] Minerals of a mixture of natural origin according to table 1 areshown in table 2.1. TABLE 2.1 Concentration Concentration ConcentrationELEMENT [mg/kg] ELEMENT [mg/kg] ELEMENT [mg/kg] Sodium 41,800 Iron 895Aluminum 1,930 Magnesium 2,130 Nickel 35 Sulfur 15,640 Calcium 19,000Copper 6 Molybdenum 16 Manganese 1,235 Chlorine 36,800 Cobalt 12Phosphor 2,110 Iodine 624 Tin <1 Mercury 2 Lead <1 Boron 194 Fluorine326 Zinc 35 Strontium 749

[0035] Minerals of a mixture (humidity 94%, ignition residue 90%) ofnatural origin are shown in table 2.2. TABLE 2.2 ConcentrationConcentration Concentration ELEMENT [mg/kg] ELEMENT [mg/kg] ELEMENT[mg/kg] Sodium 5,100 Iron 2,040 Aluminum <5 Magnesium 24,000 Nickel 14Sulfur 4,500 Calcium 350,000 Copper 10 Molybdenum 39 Manganese 125Chlorine 1,880 Cobalt 6 Phosphor 800 Iodine 181 Tin <5 Mercury <0.3 Lead460 Boron 17 Fluorine 200 Zinc 37

[0036] The material from sea animal shells can, in the case of seasediments, be used directly. If materials from the shells of crabs ormussels, lobsters, crustaceans, shrimps are used, the same is grounded.

[0037] Mixtures from sea plant materials and shells of sea animals aswell as the extracted products thereof may likewise be used. Thequantitative composition of sea plant materials and the shells of seaanimals is preferably 50 weight-% to 50 weight-%. Sea plant materialsare preferably used according to the invention.

[0038] The material from sea plants and/or shells of sea animals may bepresent in the polymer composition and the molded article producedtherefrom in an amount of 0.1 to 30 weight-%, preferably 0.1 to 15weight-%, more preferably 1 to 8 weight-%, especially 1 to 4 weight-%,based on the weight of the biologically degradable polymer. Especiallyif the molded article is present in the form of a fiber, the amount ofmaterial from sea plants and/or shells of sea animals is preferably 0.1to 15 weight-%, especially 1 to 5 weight-%.

[0039] An example for a material from sea plants used according to theinvention is a powder from Ascophyllum nodosum having a particle size of95% <40 μm, which contains 5.7 weight-% protein, 2.6 weight-% fat, 7.0weight-% fibrous components, 10.7 weight-% humidity, 15.4 weight-% ashand 58.6 weight-% carbohydrates. It moreover contains vitamins and minorelements such as ascorbic acid, tocopherols, carotene, barium, niacin,vitamin K, riboflavin, nickel, vanadium, thiamin, folic acid, folinicacid, biotin and vitamin B₁₂. In addition, it contains amino acids suchas alanine, arginine, asparagic acid, glutamic acid, glycin, leucine,lysine, serine, threonine, tyrosine, valine and methionine.

[0040] According to another embodiment the polymer composition comprisesa biologically degradable polymer and at least two components selectedfrom the group consisting of saccharides and the derivatives thereof,proteins, amino acids, vitamins and metal ions. The components may be ofsynthetic nature or of a natural origin. Said components may be used ina dried form or with a humidity, which preferably ranges between 5 and15%.

[0041] In a preferred embodiment the polymer composition comprises abiologically degradable polymer and at least three components,especially preferably at least four components, selected from the groupconsisting of saccharides and the derivatives thereof, proteins, aminoacids, vitamins and metal ions.

[0042] The polymer composition comprises especially preferably abiologically degradable polymer and at least two components selectedfrom the group consisting of saccharides and the derivatives thereof andamino acids.

[0043] The at least two components selected from the group consisting ofsaccharides and the derivatives thereof, proteins, amino acids, vitaminsand metal ions may be present in the polymer composition and the moldedarticle produced therefrom in an amount of 0.1 to 30 weight-%,preferably 0.1 to 15 weight-%, especially in an amount of 4 to 10weight-%, based on the weight of the biologically degradable polymer.

[0044] The saccharides may be used in amounts of 0.05 to 9 weight-%,preferably in amounts of 2 to 6 weight-%, the vitamins in amounts of0.00007 to 0.04 weight-%, preferably in amounts of 0.003 to 0.03weight-%, the proteins and/or amino acids in amounts of 0.005 to 4weight-%, preferably in amounts of 0.2 to 0.7 weight-%, and the metalions and the counterions thereof in amounts of 0.01 to 9 weight-%,preferably in amounts of 0.5 to 1.6 weight-%, based on the weight of thebiologically degradable polymer.

[0045] The biologically degradable polymer is preferably selected fromthe same group as in the preceding embodiment.

[0046] The saccharides or the derivatives thereof used may be selectedfrom the group consisting of monosaccharides, oligosaccharides andpolysaccharides. Mixtures containing alginic acid, laminarin, mannitoland methylpentosanes are preferably used.

[0047] The used proteins contain preferably alanine, arginine, asparagicacid, glutamic acid, glycin, leucine, lysine, serine, threonine,tyrosine, valine and methionine.

[0048] The amino acids are preferably the same ones contained in theproteins as used.

[0049] Furthermore, the used vitamins may be selected from the groupconsisting of ascorbic acid, tocopherol, carotene, niacin (vitamin B3),phytonadione (vitamin K), riboflavin, thiamin, folic acid, folinic acid,biotin, retinol (vitamin A), pyridoxine (vitamin B6) and cyanocobalamin(vitamin B₁₂).

[0050] The metal ions may be selected from the group consisting ofaluminum, antimony, barium, boron, calcium, chromium, iron, germanium,gold, potassium, cobalt, copper, lanthanum, lithium, magnesium,manganese, molybdenum, sodium, rubidium, selenium, silicon, thallium,titan, vanadium, tungsten, zinc and tin.

[0051] The counterions of the metal ions may, for example, be fluoride,chloride, bromide, iodide, nitrate, phosphate, carbonate and sulfate.The amount of metal ions or, respectively, the pertinent counterions isadjusted such that, when the at least two components or, respectively,the polymer composition are ashed, an ash content in the range of 5-95%,preferably a range of 10-60% is formed.

[0052] For the purposes according to the invention particles of thematerial from sea plants and/or shells of sea animals or the at leasttwo components selected from the group consisting of saccharides and thederivatives thereof, proteins, amino acids, vitamins and metal ions inthe particle-size range of 200 to 400 μm, preferably of 150 to 300 μmmay be used. Smaller sized particles may also be used, such as at 1 to100 μm, preferably 0.1 to 10 μm, more preferably 0.1 to 7 μm, especially1 to 5 μm (measuring method: laser diffraction apparatus: SympatecRhodos). Also grain size mixtures of a uniform material or,respectively, different algae material may be used.

[0053] In order to obtain the material from sea plants and/or shells ofsea animals or the at least two components in this fineness, thematerial from sea plants and/or shells of sea animals or the at leasttwo components may be grounded, for instance, with commerciallyavailable pin-type mills, whereupon the fine fraction is then separatedby means of corresponding classifiers. Such a classifying process fortoner for the development of electrostatic pictures is described in DE19803107, whereby a fine fraction is classified out of the product atapproximately 5 μm.

[0054] Given this process, however, only the fine fraction can beobtained, and the main fraction is thereby not used in the polymercomposition according to the invention.

[0055] Another possibility to obtain the material from sea plants and/orshells of sea animals or the at least two components in the requiredparticle size resides in disintegrating the material from sea plantsand/or shells of sea animals or the at least two components by means ofjet mills with static or rotating internal or external classifiers. Jetmills typically comprise a flat cylindrical mill chamber, around which aplurality of jet nozzles distributed about the periphery are arranged.The grinding is substantially based on a mutual exchange of kineticenergy. The disintegration achieved by particle impact is followed by aclassifying zone towards the center of the mill chamber, whereby thefine fraction is discharged by means of static or rotating internal orexternal classifiers. The coarse fraction remains in the milling spaceby means of centrifugal forces and is further grounded. A portion of thecomponents being hard to mill may be discharged from the milling spacethrough suitable apertures. Corresponding jet mills are described, forexample, in the U.S. Pat. No. 1,935,344, in EP 888818, EP 603602, DE3620440.

[0056] A typical particle size distribution is shown in FIG. 1.

[0057] The molded articles according to the invention can be producedfrom the polymer composition according to the invention withconventional methods, whereby the biologically degradable polymer andthe material from sea plants and/or shells of sea animals or the atleast two components, selected from the group consisting of saccharidesand the derivatives thereof, proteins, amino acids, vitamins and metalions are at first mixed to produce the polymer composition and themolded article can then be produced.

[0058] The continuous or discontinuous mixing of the biologicallydegradable polymer and the material from sea plants and/or shells of seaanimals or the at least two components, selected from the groupconsisting of saccharides and the derivatives thereof, proteins, aminoacids, vitamins and metal ions can take place with apparatus and on thebasis of methods described in WO 96/33221, U.S. Pat. No. 5,626,810 andWO 96/33934.

[0059] The molded article according to the invention especiallypreferably provided in the form of fibers, most preferably in the formof cellulose fibers. The molded article according to the invention mayalso be provided in the form of an endless filament, or membrane, or inthe form of a hose or a flat film.

[0060] Methods of producing the cellulose fibers according to theinvention such as the lyocell or NMMO methods, the rayon or viscosemethods or the carbamate method are known.

[0061] The lyocell method may be performed according to the followingdescription. For producing a moldable mass and the cellulose fibersaccording to the invention a solution from cellulose, NMMNO and water isproduced by first forming a suspension from cellulose, NMMNO and water,whereby said suspension is continuously transported by rotating elementsover a heat exchange surface in a layer having a thickness of 1 to 20 mmand under a reduced pressure. During this process water is evaporateduntil a homogenous cellulose solution is formed. The so obtainedcellulose solutions may contain an amount of cellulose of 2 to 30weight-%, an amount of NMMNO of 68 to 82 weight-% and an amount of waterof 2 to 17 weight-%. If desired, additives like anorganic salts,anorganic oxides, finely distributed organic substances or stabilizersmay be added to said solution.

[0062] The material from sea plants and/or shells of sea animals or theat least two components, selected from the group consisting ofsaccharides and the derivatives thereof, proteins, amino acids, vitaminsand metal ions are then continuously or discontinuously added to the soobtained cellulose solution in the form of powder, a powder suspensionor in a liquid form, as extract or suspension.

[0063] In dependence on the method the material from sea plants and/orshells of sea animals or the at least two components, selected from thegroup consisting of saccharides and the derivatives thereof, proteins,amino acids, vitamins and metal ions may also be added after or duringthe continuous disintegration of the dry cellulose, e.g. in the form ofalgae material in the original size, as powder or highly concentratedpowder suspension. The powder suspension can be produced in water or anyoptional solvent in the desired concentration required for the method.

[0064] Furthermore, it is possible to subject the material from seaplants and/or shells of sea animals or the at least two components,selected from the group consisting of saccharides and the derivativesthereof, proteins, amino acids, vitamins and metal ions to a pulpingprocess with simultaneous disintegration, or to feed to a refiner. Thepulping can be carried out either in water, in caustic solutions or inthe solvent required for dissolving the cellulose at a later stage.Here, too, the material from sea plants and/or shells of sea animals orthe at least two components, selected from the group consisting ofsaccharides and the derivatives thereof, proteins, amino acids, vitaminsand metal ions may be added in a solid, powdery, suspension-like or inliquid form.

[0065] In the presence of a derivatization agent and/or a solvent knownfor the dissolving process the polymer composition enriched with thematerial from sea plants and/or shells of sea animals or the at leasttwo components, selected from the group consisting of saccharides andthe derivatives thereof, proteins, amino acids, vitamins and metal ionscan be transferred into a moldable extrusion mass.

[0066] Another possibility of adding the material from sea plants and/orshells of sea animals or the at least two components, selected from thegroup consisting of saccharides and the derivatives thereof, proteins,amino acids, vitamins and metal ions resides in the addition during acontinuously controlled dissolving process as is described in EP 356419,U.S. Pat. No. 5,049,690 and U.S. Pat. No. 5,330,567.

[0067] Alternatively, the addition may be carried out discontinuously byobtaining a master batch of the cellulose solution. Preferably thematerial from sea plants and/or shells of sea animals or the at leasttwo components, selected from the group consisting of saccharides andthe derivatives thereof, proteins, amino acids, vitamins and metal ionsis added continuously.

[0068] The material from sea plants and/or shells of sea animals or theat least two components, selected from the group consisting ofsaccharides and the derivatives thereof, proteins, amino acids, vitaminsand metal ions may be added in any other stage of the production processfor the molded article. It can, for instance, be fed into a pipelinesystem, where it is correspondingly mixed by static mixing elements or,respectively, stirring elements such as known inline refiners orhomogenizers, e.g. apparatus from Ultra Turrax, positioned therein. Ifthe process is carried out in the continuous batch operation, e.g. bymeans of a stirred vessel cascade, the algae material can be introducedin a solid, powdery, suspension-like or liquid form at the point whichis optimal for the process. The fine distribution can be achieved withknown stirring elements adjusted to the method.

[0069] In dependence on the applied particle size the formedincorporated extrusion or spinning mass can be filtrated prior or afterthe incorporation. In response to the fineness of the applied productthe filtration may also be omitted in spinning methods using largenozzle diameters.

[0070] If the spinning masses are very sensitive, the material can, in asuited form, directly be fed upstream of the spinning nozzle or theextrusion die via an injection location.

[0071] If the algae material or the at least two components, selectedfrom the group consisting of saccharides and the derivatives thereof,proteins, amino acids, vitamins and metal ions are liquid, it isadditionally possible to feed them to the continuously spun threadduring the spinning process.

[0072] The so obtained cellulose solution is spun according toconventional methods such as the dry-jet-wet method, the wet-spinningmethod, the melt-blown method, the pot spinning method, the funnelspinning method or the dry spinning method. When the spinning takesplace according to the dry-jet-wet spinning method, the yarn sheet canalso be cooled in the air gap between the nozzle and the coagulatingbath by quenching. An air gap of 10-50 mm has proved to be suitable. Theparameters for the cooling air are preferably air temperatures of 5-35°C. with a relative humidity of up to 100%. Patent documents U.S. Pat.No. 5,589,125 and 5,939,000 as well as EP 0574870 B1 and WO 98/07911describe spinning methods for the production of cellulose fibersaccording to the NMMO method.

[0073] If required, the formed molded articles are subjected to theconventional subsequent chemical fiber treatment methods for filamentsor staple fibers.

[0074] Obtained is a cellulose fiber according to the invention with amaterial from sea plants and/or shells of sea animals or with at leasttwo components, selected from the group consisting of saccharides andthe derivatives thereof, proteins, amino acids, vitamins and metal ions,preferably at least three components, especially preferably at leastfour components.

[0075] Apart from the spinning method also extrusion methods for theproduction of flat films, round films, skins (sausage skins) andmembranes can be used.

[0076] The viscose method can be carried through as follows. Pulp withapproximately 90 to 92 weight-% of α-cellulose is treated with aqueousNaOH. Afterwards the cellulose is transformed into cellulosexanthogenate by means of conversion with carbon disulfide, and a viscosesolution is obtained by adding aqueous NaOH under constant stirring.Said viscose solution contains approximately 6 weight-% cellulose, 6weight-% NaOH and 32 weight-% carbon disulfide, based on the cellulosecontent. After the suspension was stirred, the material from sea plantsand/or shells of sea animals or the at least two components, selectedfrom the group consisting of saccharides and the derivatives thereof,proteins, amino acids, vitamins and metal ions are added either aspowder or liquid extract. If desired, common additives such assurfactants, dispersing agents or stabilizers can be added.

[0077] The material from sea plants and/or shells of sea animals or theat least two components, selected from the group consisting ofsaccharides and the derivatives thereof, proteins, amino acids, vitaminsand metal ions can, again, be added at any stage of the process.

[0078] The so obtained solution is then spun to form fibers, as is, forinstance, described in U.S. Pat. No. 4,144,097.

[0079] The carbamate method can be carried out as follows. For thispurpose, cellulose carbamate is produced from pulp with approximately 90to 95 weight-% of α-cellulose, as is described, for example, in U.S.Pat. No. 5,906,926 or in DE 19635707. Alkali cellulose is therebyproduced from the applied pulp by treating it with aqueous NaOH. Afterthe defibration the alkali cellulose is subjected to maturing and thecaustic soda solution is then washed out. The so activated cellulose ismixed with urea and water and is introduced into a solvent in a reactor.The so obtained mixture is heated. The obtained carbamate is separatedand a carbamate spinning solution is produced therefrom, which isdescribed in DE 19757958. The material from sea plants and/or shells ofsea animals or the at least two components, selected from the groupconsisting of saccharides and the derivatives thereof, proteins, aminoacids, vitamins and metal ions are added to said spinning solution.

[0080] The so obtained spinning solution is spun to form fibersaccording to known methods, and cellulose fibers according to theinvention are obtained.

[0081] It has surprisingly been found that, despite the addition of anadditive, the cellulose fibers according to the invention show the sameexcellent properties as cellulose fibers without additives, namely inview of their fineness, breaking force, breaking force variation,elongation, wet elongation, breaking tenacity, wet tenacity,fineness-related loop strength, wet abrasion upon breakage, wet abrasionvariation and wet modulus, and have, at the same time, the positiveproperties conferred by the material from sea plants and/or shells ofsea animals or the at least two components, selected from the groupconsisting of saccharides and the derivatives thereof, proteins, aminoacids, vitamins and metal ions. This is especially surprising, as theaddition of additives to spinning masses from cellulose, NMMNO and waterhas the drawback that the same discolor at the temperature ofapplication, are not resistant to storage and incorporate impuritiesinto the final cellulose products.

[0082] Furthermore, it could surprisingly be proved that the ioniccomponents incorporated with the material remain in the fiber compoundeven when subjected to a forming method with an aqueous bath liquid, anddo not escape into the spinning bath during the short spinning period.

[0083] After the spinning process the pH-value of the produced staplefiber was determined according to the DIN method 54 275. In comparisonto a fiber not incorporated with sea plants and/or shells of sea animalsthe pH-value of the incorporated fiber increased, which indicates theextraction of ionic fiber components. By said property, in connectionwith the body humidity, the bioactivity of the skin can positively andhealthfully be influenced when articles of clothing are worn.

[0084] Moreover, it has shown that by the addition of the material fromsea plants and/or shells of sea animals or the at least two components,selected from the group consisting of saccharides and the derivativesthereof, proteins, amino acids, vitamins and metal ions, thefibrillation of the fibers, produced according to the lyocell method, isreduced. Thus, the fiber according to the invention, e.g. a cellulosefiber incorporated with algae, can be applied in a more favorable mannerduring the subsequent textile treatment of the fiber.

[0085] Despite the incorporation of a material from sea plants and/orshells of sea animals or the at least two components, selected from thegroup consisting of saccharides and the derivatives thereof, proteins,amino acids, vitamins and metal ions, which is rich in iron and metalconcentrations if a sea plant is concerned, advantageously nodisintegration of a spinning solution from cellulose, NMMNO and water isobserved. It has, on the contrary, shown that the disintegrationtemperature of such a spinning solution even increased when materialfrom sea plants and/or shells of sea animals was added. This means thatdespite the presence of metal ions, no negative influence on thestability of the spinning mass could be observed.

[0086] By the incorporation of the material from sea plants and theincorporation of metals connected therewith, therefore, also chemicalreactions on the fiber material may be carried out, such as ion exchangeprocesses by the incorporated metal ions (e.g. increase of the hydrogenion concentration in the fibrous material) or the deacetylation ofchitin.

[0087] Another advantage conferred upon the molded articles according tothe invention by the addition of material from sea plants and/or shellsof sea animals or at least two components, selected from the groupconsisting of saccharides and the derivatives thereof, proteins, aminoacids, vitamins and metal ions is the homogenous incorporation of theactive substances into the fiber matrix with different produceable fiberdiameters. Moreover, the processing as monofilament or endless filamentyarn is feasible. This results in a particularly favorable applicationof technical articles.

[0088] Especially if the molded article according to the invention isproduced from a polymer composition containing exclusively biologicallydegradable material, the complete biological degradability thereof is anadvantage.

[0089] The molded articles according to the invention may be used aspackaging material, fiber material, nonwoven fabrics, textile compounds,fibrous webs, fiber fleeces, needlefelts, upholstery cotton wool, wovenfabrics, knitted fabrics, as home textiles such as bed linen, as fillingmaterial, flocking fabric, hospital textiles such as sheets, diapers ormattresses, as fabrics for heating blankets, shoe inserts and dressings.Additional possibilities of using the same are described the Dictionaryfor textile interior design [Lexikon der textilen Raumausstattung], Buchund Medien Verlag Buurmann KG, ISBN 3-98047-440-2.

[0090] If a woven fabric is produced from the molded article accordingto the invention in the form of fibers, it may either consist of saidfibers exclusively or contain an additional component. Said additionalcomponent can be selected out of the group consisting of cotton wool,lyocell, rayon, carbacell, polyester, polyamide, cellulose acetate,acrylate, polypropylene or mixtures thereof. The fibers containing amaterial from sea plants and/or shells of sea animals are present in thewoven fabric preferably in an amount of up to approximately 70 weight-%.The material from sea plants and/or shells of sea animals or the atleast two components, selected from the group consisting of saccharidesand the derivatives thereof, proteins, amino acids, vitamins and metalions are present in the woven fabric preferably in an amount of 1 to 10weight-%.

[0091] If the molded article is provided in the form of a fibrousmaterial or a woven fabric, articles of clothing such as jumpers,jackets, dresses, suits, t-shirts, underwear or the like can be producedtherefrom.

[0092] The articles of clothing produced from said fibers or wovenfabrics according to the invention are extremely comfortable to wear andin general improve the state of health of the individual wearing saidarticle of clothing. The health-improving effect of sea plant materialsis, for instance, described in JP 1228916.

[0093] Due to the high portion of negative ions in the material from seaplants and/or shells of sea animals or the at least two components,selected from the group consisting of saccharides and the derivativesthereof, proteins, amino acids, vitamins and metal ions the pH-value ofthe skin is positively influenced in as far as it arranges for alkalineand thus healthy conditions on the skin. In addition, the skintemperature is increased more when wearing the articles of clothingaccording to the invention, in contrast to wearing an article ofclothing made of fibers without the material from sea plants and/orshells of sea animals or the at least two components, selected from thegroup consisting of saccharides and the derivatives thereof, proteins,amino acids, vitamins and metal ions, whereby a positive effect isexerted on the blood circulation of the skin.

[0094] Due to the incorporated elements the fiber according to theinvention passes the active substances on to the body, namely via theliquid present during the wearing in response to the body humidity. Dueto the cellulosic material articles of clothing having good breathingproperties can thus be produced. Moreover, the active substances canpurposively be supplied to the skin, as is common in cosmetics orThalami therapy. Due to the incorporation the active substances remainin the fiber or the woven fabric for a long time, even after frequentwashing.

[0095] The minor elements and the vitamins supplied via the woven fabricmade of the fibers according to the invention can support the body dueto the remineralizing, stimulating and heating effect.

[0096] If the fiber according to the invention is provided in the formof staple fibers or disintegrated filaments, surfaces of carriers suchas woven fabrics or films can be flocked therewith. For this purpose thesurface of the carrier to be flocked is treated with an adhesive and thestaple fibers or disintegrated filaments are applied thereon.

[0097] The invention will hereinafter by explained by means of examples.

COMPARATIVE EXAMPLE 1 Without Admixture

[0098] 3,086 g NMMNO (59.8%), 308 g MoDo, DP 500, dry contents 94%,1.8propylgallate (0.63% related to the cellulose contents) were mixed, andthe so obtained mixture was heated to 94° C. Obtained was adiscontinuously produced spinning solution having a cellulose content of11.8% and a viscosity of 4,765 Pa·s. The so obtained spinning solutionwas spun to form fibers, whereby the following spinning conditions wereobserved: Temperature of the store tank 90° C. Temperature spinningblock, nozzle 80° C. Spinning bath  4° C. Spinning bath concentration(start) 0% (distilled water) Spinning bath concentration (end) 5% NMMNOSpinning pump 20.0 cm³/min. Nozzle filter 19200 M/cm² Spinning nozzle495 Hole 70 μm; Au/Pt Final drawing-off 25 m/min.

[0099] The fibers were cut to a staple length of 40 mm, were washed freeof a solvent and finished with a 10 g/l lubrication (50% Leomin OR-50%Leomin WG (nitrogen-containing fatty acid polyglycol ester ClariantGmbH)) at 45° C. or, respectively, the fat add-on for the bettercontinued processing of the fibers was applied, and dried at 105° C.Subsequent to the drying a fiber humidity of 11% was adjusted. Anadditional bleaching process prior to the drying was not performed inthis case.

[0100] The spinning behavior of the spinning solution obtained accordingthe present example was good. TABLE 3 Fiber data comparative example 1Comparative Example 1 Fineness - Titer [dtex] 1.48 Breaking tenacity dry[cN/tex] 42.20 Breaking tenacity wet [cN/tex] 36.30 Breaking tenacityloop [cN/tex] 15.20 Breaking elongation - dry [%] 15.50 Breakingelongation - wet [%] 15.20 Wet modulus [cN/tex] 202.00

COMPARATIVE EXAMPLE 2 Without Admixture: Treatment of the Filaments inthe Air Gap

[0101] The spinning solution was produced analogously to comparativeexample 1. The spinning solution was spun to fibers, whereby, indeviation from comparative example 1, the temperature of the spinningblock was adjusted to 95° C. and the temperature of the nozzle to 105°C. In the air gap between the nozzle and the coagulating bath the yarnsheet was quenched with humid air (temperature: 20° C., humidity: 70%).

[0102] Otherwise, the test performance was carried out like incomparative example 1. TABLE 4 Fiber data comparative example 2Comparative Example 2 Fineness - Titer [dtex] 1.25 Breaking tenacity dry[cN/tex] 45.10 Breaking tenacity wet [cN/tex] 37.10 Breaking tenacityloop [cN/tex] 22.10 Breaking elongation - dry [%] 15.40 Breakingelongation - wet [%] 18.50 Wet modulus [cN/tex] 234.00

EXAMPLE 1

[0103] 3,156 g NMMNO (61.4%), 315 g MoDo, DP 500, dry contents 94%, 1.9g propylgallate (0.63% related to the cellulose content) as well as 11.6g of a powder—shown in table 1—(in total 3.9% related to the cellulosecontent) were mixed and heated to 94° C. Obtained was a spinningsolution having a solids content of 12.4% and a viscosity of 6,424 Pa·s.The so produced spinning solution was spun to fibers like in comparativeexample 1, TABLE 5 Fiber data example 1 Example 1 Fineness - Titer[dtex] 1.40 Breaking tenacity dry [cN/tex] 38.60 Breaking tenacity wet[cN/tex] 30.70 Breaking tenacity loop [cN/tex] 11.40 Breakingelongation - dry [%] 12.40 Breaking elongation - wet [%] 13.00 Wetmodulus [cN/tex] 199.00

EXAMPLE 2

[0104] Analogously to example 1, 2.951 g NMMNO (60.84%), 305 g MoDo, DP500, dry contents 94%, 1.8 g propylgallate (0.63% related to thecellulose content) as well as 17.5 g of the mixture used in table 1—(intotal 6.1% related to the cellulose content) were mixed and heated to94° C. Obtained was a spinning solution having a solids content of 12.9%and a viscosity of 7.801 Pa·s. The so produced spinning solution wasspun to fibers like in comparative example 1. TABLE 6 Fiber data example2 Example 2 Fineness - Titer [dtex] 1.48 Breaking tenacity dry [cN/tex]36.60 Breaking tenacity wet [cN/tex] 32.40 Breaking tenacity loop[cN/tex] 13.30 Breaking elongation - dry [%] 12.10 Breaking elongation -wet [%] 13.50 Wet modulus [cN/tex] 188.00

EXAMPLE 3

[0105] Analogously to example 1, 2,750 g NMMNO (60.3%), 305 g MoDo, DP500, dry contents 94%, 1.7 g propylgallate (0.63% related to thecellulose content) as well as 11.2 g of a powder—shown in table 2.2— (intotal 4.1% related to the cellulose content) were mixed and heated to94° C. Obtained was a spinning solution having a solids content of 13%and a viscosity of 6.352 Pa·s. The so produced spinning solution wasspun to fibers like in comparative example 1. TABLE 7 Fiber data example3 Example 3 Fineness - Titer [dtex] 1.41 Breaking tenacity dry [cN/tex]33.40 Breaking tenacity wet [cN/tex] 29.20 Breaking tenacity loop[cN/tex] 9.00 Breaking elongation - dry [%] 12.60 Breaking elongation -wet [%] 8.60 Wet modulus [cN/tex] 182.00

EXAMPLE 4

[0106] Analogously to example 3, 3,345 g NMMNO (59.5%), 318 g MoDo, DP500, dry contents 94%, 1.9 g propylgallate (0.63% related to thecellulose content) as well as 23.6 g of a mixture similar to the oneused in table 3 (in total 7.9% related to the cellulose content) weremixed and heated to 94° C. The mixture used in this example differs fromthe one used in example 3 above all by a higher potassium content and alower calcium content (˜12.6% to ˜35%). Obtained was a spinning solutionhaving a solids content of 12.4% and a viscosity of 7.218 Pa·s. The soproduced spinning solution was spun to fibers like in comparativeexample 1. TABLE 8 Fiber data example 4 Example 4 Fineness - Titer[dtex] 1.42 Breaking tenacity dry [cN/tex] 41.40 Breaking tenacity wet[cN/tex] 32.90 Breaking tenacity loop [cN/tex] 8.30 Breakingelongation - dry [%] 11.90 Breaking elongation - wet [%] 12.00 Wetmodulus [cN/tex] 212.00

EXAMPLE 5

[0107] 3,204 g NMMNO (59.5%), 318 g MoDo, DP 500, dry contents 94.4%,1.9 g propylgallate (0.63% related to the cellulose content) and 25.4 gbrown algae (8.5% related to the cellulose content) of the typeLaminaria were mixed, and the so obtained mixture was heated to 94° C.Obtained was a discontinuously produced spinning solution having acellulose content of 13.24% and a viscosity of 6.565 Pa·s. The soobtained spinning solution was spun to fibers, whereby the followingspinning conditions were observed: Temperature of the store tank 90° C.Temperature spinning block, nozzle 80° C. Spinning bath  4° C. Spinningbath concentration (start) 0% (distilled water) Spinning bathconcentration (end) 7% NMMNO Spinning pump 20.0 cm³/min. Nozzle filter19200 M/cm² Spinning nozzle 495 Hole 70 μm; Au/Pt Final drawing-off 30m/min.

[0108] The fibers were cut to a staple length of 40 mm, were washed freeof a solvent and finished with a 10 g/l lubrication (50% Leomin OR-50%Leomin WG (nitrogen-containing fatty acid polyglycol ester ClariantGmbH)) at 45° C. or, respectively, the fat add-on for the bettercontinued processing of the fibers was applied, and dried at 105° C.Subsequent to the drying a fiber humidity of 10% was adjusted. Anadditional bleaching process prior to the drying was not performed inthis case.

[0109] The spinning behavior of the spinning solution obtained accordingthe present example was good.

[0110] The following table 9 shows the physical properties of the soobtained cellulose fibers. TABLE 9 Fineness [dtex] 1.42 Breaking force[cN] 5.85 Breaking force variation [%] 15.8 Elongation [%] 11.9 Wetelongation [%] 12.0 Breaking tenacity [cN/tex] 41.4 Breaking tenacitywet [cN/tex] 32.9 Loop breaking tenacity [cN/tex] 8.3 Wet abrasion uponbreakage [turns] 10 Wet abrasion variation [%] 19.7 Wet modulus [cN/tex]212

[0111] The elementary analyses of the applied material from sea plants,brown algae Laminaria digitata and the fiber sample with incorporatedbrown algae is shown in the following table 10. TABLE 10 Fiber samplewith incorporated Brown algae brown algae material Analyses [mg/kg]material Laminaria digitata Sodium 28,300 460 Magnesium 51,300 3,400Calcium 126,000 8,100 Chromium 850 50 Manganese 670 55 Iron 32,600 2,000Nickel 210 20 Copper 30 8 Molybdenum <5 <5 Cobalt 19 <5

[0112]FIG. 2 moreover shows that a spinning solution with 8.5% Laminariadigitata is stable over thermal disintegration up to approximately 200°C.

EXAMPLE 6

[0113] 3,687 g NMMNO (62%), 381 g MoDo, DP 500, dry contents 94.4%, 2.27g propylgallate (0.63% related to the cellulose content) and 3.6 g brownalgae flour Laminaria digitata (1% related to the cellulose content)were mixed and heated to 94° C. Obtained was a spinning solution havinga cellulose content of 12.78% and a viscosity of 8.424 Pa·s. The soproduced spinning solution was spun to fibers like in comparativeexample 1.

[0114] The physical properties of the so obtained cellulose fibers areshown in the following table 11. Fineness [dtex] 1.40 Breaking force[cN] 6.10 Breaking force variation [%] 21.8 Elongation [%] 13.0 Wetelongation [%] 12.7 Breaking tenacity [cN/tex] 42.4 Breaking tenacitywet [cN/tex] 37.7 Loop breaking tenacity [cN/tex] 8.81 Wet abrasion uponbreakage [turns] 14 Wet abrasion variation [%] 34.7 Wet modulus [cN/tex]254

[0115] The so obtained fibers were spun to a yarn. The spinning wascarried out under the conditions 63% relative air humidity and 20° C. bymeans of carding, stretching and spinning with a rotor spinning machine,to form 75 g of yarn with approximately 20 tex. FIG. 3 shows that thespinning solution with 1% Laminaria digitata, related to the cellulosecontent, is stable up to a temperature of approximately 200° C.

EXAMPLE 7

[0116] A cellulose xanthogenate was produced from a mixture of 33weight-% cellulose, 17 weight-% caustic soda solution and 50 weight-%water by adding 32% carbon disulfide related to cellulose. Thereafterthe xanthogenate was transferred by stirring for 2 hours, with theaddition of diluted caustic soda solution, into a spinning solution with6 weight-% cellulose, 6 weight-% NaOH and substantially water andreaction products resulting from the xanthate production. To the soobtained viscose solution 0.9 weight-% of brown algae material wereadded to the spinning solution. The viscose solution was allowed tostand for approximately 6 hours under a vacuum for degassing andthereupon filtrated. The so obtained viscose solution had a maturitylevel of 10° Hottenroth and was spun to fibers.

[0117] The spinning conditions were: Nozzle [n/μm] 1,053/60 Holethroughput [g/hole/min.] 0.07 Temperature of coagulating bath [° C.] 30Sulfuric acid in the coagulating bath [%] 10.8 Sodium sulfate in thecoagulating bath [%] 20.0 Zinc sulfate in the coagulating bath [%] 1.5Drawing-off speed [m/min.] 36

[0118] The physical properties of the so obtained rayon fibers are shownin the following table 12. TABLE 12 Fineness - Titer [dtex] 1.7 Breakingtenacity dry [cN/tex] 21.7 Breaking tenacity wet [cN/tex] 12.4Fineness-related loop strength [cN/tex] 6.0 Breaking elongation - dry[%] 14.2 Breaking elongation - wet [%] 15.8 Wet modulus [cN/tex] 2.9

EXAMPLE 8

[0119] Rayon fibers were produced in accordance with example 7, exceptfor the fact that 0.1 weight-% of brown algae material instead of 0.9weight-% were added to the spinning solution.

[0120] The physical properties of the so obtained viscose or rayonfibers are shown in table 13. TABLE 13 Fineness - Titer [dtex] 1.7Breaking tenacity dry [cN/tex] 23.7 Breaking tenacity wet [cN/tex] 14.1Loop strength [cN/tex] 6.5 Breaking elongation - dry [%] 16.9 Breakingelongation - wet [%] 18.5 Wet modulus [cN/tex] 3.0

COMPARATIVE EXAMPLE 3

[0121] As comparison, a viscose fiber was produced in accordance withexample 7, except for the fact that no brown algae material was added.

[0122] The physical properties of said viscose fiber are shown in table14. TABLE 14 Fineness - Titer [dtex] 1.7 Breaking tenacity dry [cN/tex]24.8 Breaking tenacity wet [cN/tex] 14.2 Loop strength [cN/tex] 6.4Breaking elongation - dry [%] 17.2 Breaking elongation - wet [%] 21.1Wet modulus [cN/tex] 2.9

EXAMPLE 9

[0123] For the production of cellulose carbamate an alkali cellulose wasfirst produced from a chemical pulp with 92-95% alpha-content(Ketchikan). The caustic soda solution was washed out of the maturedalkali cellulose (35 weight-% cell; 15 weight-% NaOH; 50 weight-% water)with water. After squeezing out the so activated cellulose (70 weight-%water) 10 kg of the squeezed out activated cellulose were mixed withurea (1.5 kg) in a kneader. The urea is thereby separated in the watercontained in the cellulose and is evenly distributed in the cellulose.Said cellulose pulp was transferred into a reactor equipped with stirrerand reflux cooler, into which o-xylol (30 kg) had been fed. The contentsin the reactor was then heated for approximately 2 hours at 145° C. andfiltered off.

[0124] The so obtained residue was passed back into the reactor, intowhich approximately 25 kg water had been fed. The xylol still adheringto the carbamate was stripped off at 88° C. After the filtration thecarbamate was washed out with hot water (50° C.) and with cold water.Thereafter the carabamate was squeezed out.

[0125] 3.45 kg Stark-solution were produced from 1.02 kg of saidcarbamate with 1.1 kg caustic soda solution (30 weight-%), 1.30 kg waterand with the corresponding amount of brown algae (0.03 kg). Allreactants were pre-cooled. The reaction itself took place at atemperature of 0° C. (Composition of the Stark-lye: 11.0 weight-% cell,9.5 weight-% NaOH).

[0126] A spinning mass (5 kg) was produced from the cooledStark-solution by adding 1.55 kg cooled caustic soda solution (3.03weight-%) at a temperature of 0° C. The cooled spinning mass wasfiltrated through a filter with degrees of fineness of 10-40 μm and wasspun.

[0127] The following spinning conditions were observed: Nozzle [n/μm]36/60 Hole throughput [g/hole/min.] 0.11 Temperature of coagulating bath[° C.] 35 Sulfuric acid in the coagulating bath [%] 90 Sodium sulfate inthe coagulating bath [%] 140 Drawing-off speed [m/min.] 30

[0128] The physical properties of the so obtained Carbacell® fibers areshown in table 15. TABLE 15 Fineness - Titer [dtex] 3.1 Breakingtenacity dry [cN/tex] 14.8 Breaking tenacity wet [cN/tex] 5.7 Loopstrength [cN/tex] 7.5 Breaking elongation - dry [%] 4.0 Breakingelongation - wet [%] 4.7 Wet modulus [cN/tex] 100

EXAMPLE 10

[0129] Carbacell® fibers were produced in accordance with example 9,except for the fact that 0.1 weight-% of brown algae flour instead of0.6 weight-% were added to the spinning mass.

[0130] The physical properties of the so obtained Carbacell® fibers areshown in the following table 16. Fineness - Titer [dtex] 3.3 Breakingtenacity dry [cN/tex] 17.8 Breaking tenacity wet [cN/tex] 5.8 Loopstrength [cN/tex] 7.5 Breaking elongation - dry [%] 4.6 Breakingelongation - wet [%] 5.4 Wet modulus [cN/tex] 129

COMPARATIVE EXAMPLE 4

[0131] Carbacell® fibers were produced in accordance with example 9,except for the fact that no brown algae flour was added.

[0132] The physical properties of the so obtained fibers are shown inthe following table 17. TABLE 17 Fineness - Titer [dtex] 3.1 Breakingtenacity dry [cN/tex] 18.0 Breaking tenacity wet [cN/tex] 5.8 Loopstrength [cN/tex] 7.9 Breaking elongation - dry [%] 4.7 Breakingelongation - wet [%] 5.5 Wet modulus [cN/tex] 135

EXAMPLES 11 TO 15

[0133] Lyocell cellulose fibers were continuously produced in accordancewith example 5, whereby the respective amounts, the conditions of thecontinuously performed process and the physical properties of theobtained fibers are shown in the following table 18. TABLE 18 ExampleExample Example Example Example Unit 11 12 13 14 15 Pulp Type AlicellModo Alicell Alicell Alicell VLV Drown VLF VLV VLV Dissolving DP Pulp 9540 530 540 540 540 Feed hole kg/h 161.8 161.8 173.0 167.2 161.7Cellulose % 13.0% 13.0% 12.0% 12.5% 13.0% Water % 10.7% 10.7% 11.3%11.0% 10.7% NMMO % 76.3% 76.3% 76.7% 76.5% 76.3% Solution flow kg/h138.5 138.5 150.0 144.0 138.5 Vapor kg/h 23.3 23.3 23.0 23.2 23.3condensate System pressure mbar 55 55 55 55 55 abs. Spinning temp. ° C.117 110 72 80 117 Fiber draft 10.9 10.9 4.3 10.5 11.81 Titer dtex 1.31.3 1.3 1.3 1.18 Air gap height mm 20 20 7 12 20 Air quantity Nm³/h 130130 130 180 135 Air temperature ° C. 17.5 18.5 17.2 17.9 19 Holethroughput g/hole 0.030 0.060 0.028 0.134 0.028 min Hole diameter μ 100100 65 100 100 Brown algae g/h 181.9 182.3 1528.0 1531.8 2704.0 powderAmount Coagulating bath ° C. 20 20 6 6 20 temperature Spinning bath % 2020 20 20 20 concentration NMMO Final drawing-off m/mm 35 70 30 150 35Titer dtex 1.40 1.42 1.38 1.40 1.21 Strength dry cn/tex 42.1 41.4 41.842.4 41 Elongation dry % 12.8 11.9 13.0 13.2 13.8 Wet strength cn/tex32.9 34.8 37.7 37.7 33.4 Wet elongation % 12.0 12.3 12.7 12.0 12.8 Loopstrength cn/tex 15.4 13 8.3 8.9 13.8 Wet modulus cn/tex 238 254 212 212242

EXAMPLE 16

[0134] Based on the fibers produced in accordance with comparativeexample 1 and 2 and in accordance with examples 1 to 4 cryo-breaks inliquid nitrogen were produced, whereof photographs were taken by meansof a field emission electron-scanning microscope (Joel 6330 F) after thefibers had been sputtered with platinum.

[0135] The fiber produced according to comparative example 1 or 2according to the standard process shows a splinted break. The fibrillarystructure can clearly be recognized on the broken surface. The strongorientation of the fibrilla can be seen on the standing out longitudinalridges and on the strongly fissured structure along the longitudinalaxis.

[0136] The photographs of the fibers from examples 1 to 4 show somethingcompletely different. The partly blunt and clean broken surfaces canclearly be recognized. Moreover, it can be recognized that the distincthigh longitudinal orientation in the fiber according to comparativeexample 1 is much less distinct in examples 1 to 4.

[0137] On the basis of the electron-scanning microscope photographsstriking differences in the structure of the fiber were detected.

[0138] Above all, the strongly repressed longitudinal orientation showsthat the use according to the invention of material from sea plantsand/or shells of sea animals or of at least two components selected fromthe group consisting of saccharides and the derivatives thereof,proteins, amino acids, vitamins and metal ions results in a smallerfibrillation of the fibers during the production of cellulose fibers.

[0139] It had been especially interesting and unexpected that mixtureswith different substances contained therein show said effect, as allpreviously known defibrillation agents are cross-linking agents. Thesmaller fibrillation is presumably due to a change of thecrystallization properties of the cellulose during the extrusion.

1. Polymer composition comprising a biologically degradable polymer anda material from sea plants and/or shells of sea animals:
 2. Polymercomposition according to claim 1, wherein the material from sea plantsis selected from the group consisting of algae, kelp, seaweed andmixtures thereof.
 3. Polymer composition according to claim 2, whereinthe material from sea plants is selected from the group consisting ofbrown algae, green algae, red algae, blue algae and mixtures thereof. 4.Polymer composition according to one of the preceding claims, whereinthe material from the shells of sea animals is selected from the groupconsisting of sea sediments and grounded shells of crabs, lobsters,crustaceans and mussels and mixtures thereof.
 5. Polymer compositionaccording to one of the preceding claims, wherein the material from seaplants and/or shells of sea animals is provided in an amount of 0.1 to30 weight-% based on the weight of the biologically degradable polymer.6. Polymer composition according to one of the preceding claims, whereinthe biologically degradable polymer is cellulose and the material fromsea plants are algae.
 7. Polymer composition comprising a biologicallydegradable polymer and at least two components selected from the groupconsisting of saccharides and the derivatives thereof, proteins, aminoacids, vitamins and metal ions.
 8. Polymer composition according toclaim 7, wherein at least three components are present.
 9. Polymercomposition according to claim 7, wherein at least four components arepresent.
 10. Polymer composition according to one of claims 7 to 9,wherein the at least two components are provided in an amount of 0.1 to30 weight-% based on the weight of the biologically degradable polymer.11. Polymer composition according to one of claims 7 to 10, wherein theat least two components are selected from the group consisting ofsaccharides and the derivatives thereof and amino acids.
 12. Polymercomposition according to one of the preceding claims, wherein thebiologically degradable polymer is selected from the group consisting ofcellulose, modified cellulose, latex, vegetable and animal protein, andmixtures thereof.
 13. Molded article comprising a polymer compositionaccording to one of the preceding claims.
 14. Molded article accordingto claim 13, wherein the molded article is selected from the groupconsisting of tanks, films, membranes, woven fabrics and fibers. 15.Molded article according to claim 14, wherein the fibers are staplefibers, monofilaments or endless filaments.
 16. Use of the moldedarticle according to one of claims 13 to 15 as packaging material orfibrous material.
 17. Use of the molded article according to one ofclaims 13 to 15 in the form of a fibrous material as mixing componentfor the production of yarns.
 18. Use of the molded article according toone of claims 13 to 15 in the form of a fibrous material for theproduction of nonwoven fabrics or woven fabrics.
 19. Use of the moldedarticle according to one of claims 13 to 15 in the form of a fibrousmaterial for the production of nonwoven fabrics or woven fabrics,wherein a component selected from the group consisting of cotton wool,lyocell, rayon, carbacell, polyester, polyamide, cellulose acetate,acrylate, polypropylene or mixtures thereof is additionally present inthe nonwoven fabric or woven fabric.
 20. Use of the molded articleaccording to claim 19, wherein 0.1 to 30 weight-% of the additionalcomponent are contained.
 21. Woven fabric comprising a molded articleaccording to one of claims 13 to
 15. 22. Nonwoven fabric comprising amolded article according to one of claims 13 to
 15. 23. Article ofclothing comprising a molded article according to one of claims 13 or15.
 24. Method of producing a molded article according to one of claims13 to 15, comprising the following steps: (A) continuously ordiscontinuously mixing the biologically degradable polymer and thematerial from sea plants and/or shells of sea animals or the at leasttwo components selected from the group consisting of saccharides and thederivatives thereof, proteins, amino acids, vitamins and metal ions, (B)producing a moldable mass, (C) processing the mass obtained in (B) toform a molded article, and (D) subsequently treating the produced moldedarticle.
 25. Method according to claim 24, wherein a molded articleaccording to one of claims 13 to 15 is produced.